Aluminum silicate, metal ion adsorbent, and method for producing same
View Patent ↗The aluminum silicate of the invention has: an element ratio of Si and Al, represented by Si/Al, of from 0.3 to 1.0 by molar ratio; a peak at approximately 3 ppm in a 27 Al-NMR spectrum; peak A at approximately −78 ppm and peak B at approximately −85 ppm in a 29 Si-NMR spectrum; and a peak at approximately 2θ=26.9° and a peak at approximately 2θ=40.3° in a powder X-ray diffraction spectrum. The aluminum silicate has an area ratio of peak B with respect to peak A of from 2.0 to 9.0, or does not include a tubular substance having a length of 50 nm or more as observed in a transmission electron microscope (TEM) photograph of the aluminum silicate taken at a magnification of 100,000. The aluminum silicate is produced by a method comprising: subjecting a reaction product of a silicate ion solution and an aluminum ion solution to desalting and solid separation; subjecting a resultant to a thermal treatment in an aqueous medium in the presence of an acid under concentration conditions in an aqueous medium such that a silicon atom concentration is 100 mmol/L or more and an aluminum atom concentration is 100 mmol/L or more; and subjecting a resultant to further desalting and solid separation.
1. An aluminum silicate, having:
an element ratio of Si and Al, represented by Si/Al, of from 0.3 to 1.0 by molar ratio;
a peak at approximately 3 pmm in a 27 Al-NMR spectrum;
a peak at approximately −78 ppm and a peak at approximately −85 ppm in a 29 Si-NMR spectrum;
peaks at approximately 2θ=26.9°, 18.8°, 20.3°, 27.8°, 40.3°, 40.6° and 53.3° in a powder X-ray diffraction spectrum in which a CuKα ray is used as an X-ray source; and
an area ratio of peak A and peak B, represented by peak B/peak A, of from 2.0 to 9.0, wherein peak A is at approximately −78 ppm and peak B is at approximately −85 ppm, in a 29 Si-NMR spectrum.
2. The aluminum silicate according to claim 1 , wherein the aluminum silicate does not comprise a tubular substance having a length of 50 nm or more as observed in a transmission electron microscope (TEM) photograph of the aluminum silicate taken at a magnification of 100,000.
3. The aluminum silicate according to claim 1 , wherein the aluminum silicate has a BET specific surface area of 250 m 2 /g or more, a total pore volume of 0.1 cm 3 /g or more, and an average pore diameter of 1.5 nm or more.
4. A method of producing the aluminum silicate according to claim 1 , the method comprising:
(a) a process of obtaining a reaction product by mixing a solution that includes silicate ions and solution that includes aluminum ions;
(b) a process subjecting the reaction product to desalting and solid separation;
(c) a process of subjecting a resultant of the solid separation in process (b) to a thermal treatment in an aqueous medium in the present of an acid, under concentration conditions such that a silicon atom concentration is 100 mmol/L or more and an aluminum atom concentration is 100 mmol/L or more; and
(d) a process of subjecting a resultant of the thermal treatment in process (c) to desalting and solid separation.
5. The method of producing the aluminum silicate according to claim 4 , wherein the resultant of the solid separation in process (b) has an electric conductivity of 4.0 S/m or less when the resultant is dispersed in water such that a concentration of the resultant is 60 g/L.
6. The method of producing the aluminum silicate according to claim 4 , wherein the thermal treatment in process (c) is performed with a pH of from 3 to less than 7, at a temperature of from 80° C. to 160° C. and for time of within 96 hours.
7. The method for producing the aluminum silicate according to claim 4 , wherein in process (a), the solution that includes silicate ions has a silicon atom concentration of 100 mmol/L or more, the solution that includes aluminum ions has an aluminum atom concentration of 100 mmol/L, and the mixing is performed such that an element ration of the aluminum with to silicon, represented by Si/Al, is from 0.3 to 1.0 by molar ratio.
8. The method of producing the aluminum silicate according to claim 4 , wherein process (b) comprises a process of obtaining a dispersion by dispersing the reaction product in an aqueous medium and a process of performing solid separation with a pH of the dispersion adjusted to from 5 to 7.
9. An aluminum silicate, having:
an element ratio of Si and Al, represented by Si/Al, of from 0.3 to 1.0 by molar ratio;
a peak at approximately 3 pmm in a 27 Al-NMR spectrum;
a peak at approximately −78 ppm and a peak at approximately −85 ppm in a 29 Si-NMR spectrum; and
peaks at approximately 2θ=26.9, 18.8°, 20.3°, 27.8°, 40.3°, 40.6° and 53.3° in a powder X-ray diffraction spectrum in which a CuKα ray is used as an X-ray source,
the aluminum silicate not comprising a tubular substance having a length of 50 nm or more as observed in a transmission electron microscope (TEM) photograph of the aluminum silicate taken at a magnification of 100,000.
10. The aluminum silicate according to claim 9 , wherein aluminum silicate has a BET specific surface area of 250 m 2 /g or more, a total pore volume of 0.1 cm 3 /g or more, and an average pore diameter of 1.5 nm or more.
11. A metal ion adsorbent, comprising an aluminum silicate having:
an element ratio of Si and Al, represented by Si/Al, of from 0.3 to 1.0 by molar ratio;
a peak at approximately 3 pmm in a 27 Al-NMR spectrum;
a peak at approximately −78 ppm and a peak at approximately −85 ppm in a 29 Si-NMR spectrum;
an area ratio of peak A and peak B, represented by peak B/peak A, of from 2.0 to 9.0, wherein peak A is at approximately −78 ppm and peak B is at approximately −85 ppm, in a 29 Si-NMR spectrum; and
peaks at approximately 2θ=26.9°, 18.8°, 20.3°, 27.8°, 40.3°, 40.6° and 53.3° in a powder X-ray diffraction spectrum in which a CuKα ray is used as an X-ray source.
12. The metal ion adsorbent according to claim 11 , wherein the aluminum silicate does not comprise a tubular substance having a length of 50 nm or more as observed in a transmission electron microscope (TEM) photograph of the aluminum silicate taken at a magnification of 100,000.
13. The metal ion adsorbent according to claim 11 , wherein the aluminum silicate has a BET specific surface area of 250 m 2 /g or more, a total pore volume of 0.1 cm 3 /g or more, and an average pore diameter of 1.5 nm or more.
14. A method of producing the metal ion adsorbent according to claim 11 , the comprising:
(a) a process of obtaining a reaction product by mixing a solution that includes silicate ions and solution that includes aluminum ions;
(b) a process subjecting the reaction product to desalting and solid separation;
(c) a process of subjecting a resultant of the solid separation in process (b) to a thermal treatment in an aqueous medium in the present of an acid; and
(d) a process of subjecting a resultant of the thermal treatment in process (c) to desalting and solid separation.
15. The method of producing the aluminum silicate according to claim 14 , wherein the treatment in process (c) is performed under concentration conditions in the aqueous medium such that a silicon atom concentration is 100 mmol/L or more and an aluminum atom concentration is 100 mmol/L or more.
16. The method of producing the metal ion adsorbent according to claim 14 , wherein the resultant of the solid separation in process (b) has an electric conductivity of 4.0 S/m or less when the resultant is dispersed in water such that a concentration of the resultant is 60 g/L.
17. The method of producing the metal ion adsorbent according to claim 14 , wherein the thermal treatment in process (c) is performed with a pH of from 3 to less than 7, at a temperature of 80° C. to 160° C. and for a time of within 96 hours.
18. The method of producing the metal ion adsorbent according to claim 14 , wherein in process (a), the solution that includes silicate ions has a silicon atom concentration of 100 mmol/L or more, the solution that includes aluminum ions has an aluminum atom concentration of 100 mmol/L, and the mixing is performed such that an element ration of the aluminum with to silicon, represented by Si/Al, is from 0.3 to 1.0 by molar ratio.
19. The method of producing the metal ion adsorbent according to claim 14 , wherein process (b) comprises a process of obtaining a dispersion by dispersing the reaction product in an aqueous medium and a process of performing solid separation with a pH of the dispersion adjusted to from 5 to 7.